Research Article

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Mg(OH)2 Supported Nanoscale Zero Valent Iron Enhancing the

Removal of Pb(II) from Aqueous Solution
Minghui Liu,†,∥ Yonghao Wang,†,‡,∥ Luntai Chen,†,∥ Yan Zhang,†,∥ and Zhang Lin*,†,§,∥
†
Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou, Fujian 350002, China
‡
College of Environment and Resources, Fuzhou University, Fuzhou, Fujian 350002, China
§
School of Environment and Energy, South China University of Technology, Guangzhou 510006, China
∥
Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of
Sciences, Fuzhou, Fujian 350002, China
*
S Supporting Information

ABSTRACT: In this article, a novel composite (Mg(OH)2

supported nanoscale zerovalent iron (denoted as nZVI@Mg-
(OH)2) was prepared and characterized by X-ray diffraction,
scanning electron microscopy, and transmission electron micros-
copy method. The morphology analysis revealed that Mg(OH)2
appeared as self-supported flower-like spheres, and nano Fe0
particles were uniformly immobilized on the surface of their
“flower petals”, thus aggregation of Fe0 particles was minimized.
Then the Pb(II) removal performance was tested by batch
experiments. The composite presented exceptional removal
capacity (1986.6 mg/g) compared with Mg(OH)2 and nanoscale
zerovalent iron due to the synergistic effect. Mechanisms were also
explored by a comparative study of the phase, morphology, and
surface valence state of composite before and after reaction, indicating that at least three paths are involved in the synergistic
removal process: (1) Pb(II) adsorption by Mg(OH)2 (companied with ion exchange reaction); (2) Pb(II) reduction to Pb0 by
nanoscale zerovalent iron; and (3) Pb(II) precipitation as Pb(OH)2. The hydroxies provided by Mg(OH)2 can dramatically
promote the role of nanoscale zerovalent iron as reducer, thus greatly enhancing the whole Pb(II) sequestration process. The
excellent performance shown in our research potentially provides an alternative technique for Pb(II) pollution treatment.
KEYWORDS: nanoscale zerovalent iron (nZVI), magnesium hydroxide, nZVI@Mg(OH)2 composite, synergistic sequestration

■ INTRODUCTION
Lead can cause acute, chronic circulatory, neurological,
hematological, gastrointestinal, reproductive, and immunolog-
ical pathologies,1−3 because of its toxicity and nonbiodegrad-
ability. In China, some industrial processes including lead
mining, smelting, and consuming can discharge lead-bearing
wastewater, especially in the lead-acid batteries industry, where
over 20 million tons of wastewater are generated per year,
containing more than 150 tons of Pb(II). Therefore, a cost-
effective method must be developed to treat Pb(II)-bearing
wastewater.
At present, extensive methods have been employed to
remedy heavy metal polluted wastewater, including chemical
precipitation, ion-exchange, membrane separation, and adsorp-
tion.4−6 Among them, adsorption is considered as one of the
most attractive ways due to its easy processability and high
efficiency. In the past two decades, nanoscale zerovalent iron
(nZVI) has received much attention because of its large specific
surface area, high reaction activity, and strong reductive
power.7,8 Studies show that nZVI appears to be effective in
removing various pollutants, such as chlorinated organic
compounds,9 nitroaromatic compounds,10 dyes,11 and heavy
metal ions,12−15 including Pb(II).16−21 Nevertheless, nZVI
particles tend to aggregate due to the high surface energy and
magnetic force, leading to sharp deterioration of activity,
durability, and efficiency, which would greatly hinder the large-
scale application of nZVI.22 Incorporating nZVI particles onto
support materials can successfully ease the above-mentioned
problems. The commonly used support materials include
kaolinite,11,17 zeolite,20 clay,23,24 bentonite25 and chelating
resin,16 mesoporous carbon,10,14 silica,9 and graphene,26
which all can reduce the aggregation of nZVI particles, thus
improving their performance in pollutant treatment. However,
some shortcomings of the reported support materials, such as
complexity of preparation, high cost, and uneven loading, still
limit the wide application of nZVI. Hence, the ideal carrier to
Received: December 30, 2014
Accepted: March 31, 2015
Published: March 31, 2015

© 2015 American Chemical Society 7961 DOI: 10.1021/am509184e

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fulfill the potential of nZVI must be cost-effective, mechanically
stable, and compatible with nZVI particles. Especially, an
intense affinity of support material toward target ions will
definitely enhance the performance of nZVI as a whole.
In recent years, nanoscale magnesium hydroxide (Mg(OH)2)
has aroused extensive attention because of low-cost and
environmental friendliness. Researches indicate that Mg(OH)2
exhibits a promising prospect in acid wastewater treatment,
heavy metal deprivation,27 and decoloration of printing and
dyeing wastewater. For instance, Wang et al.28 demonstrated
that nanoscale self-supported Mg(OH)2 aggregates could
absorb low concentration anionic dye from water selectively.
Li et al.29 reported that self-supported flowerlike Mg(OH)2
could recycle rare earth ion from low concentration wastewater
via ion-exchange. All those researches reveal that the
morphology of Mg(OH)2 can be easily controlled and modified
to obtain a self-supported flowerlike structure with large specific
surface area, which can potentially provide an ideal carrier for
nZVI particles.30 Based on the potential attraction of Mg(OH)2
to Pb(II), we expected the combination of nZVI and Mg(OH)2
could allow a synergy more than reducing aggregation of nZVI
particles, which would facilitate decontamination of Pb(II).
In this article, we aim to develop a novel composite by
loading nZVI onto Mg(OH)2 (nZVI@Mg(OH)2). The
performance of removing Pb(II) was investigated by batch
experiments. In addition, the influence of Fe loading ratio, pH
value, and initial Pb(II) concentration on removal efficiency
were also tested. The results show that the agglomeration of
nZVI particles was eliminated, and a superb capacity for Pb(II)
uptake was achieved (1986.6 mg/g), much higher than the
weighted sum value (1246 mg/g) of its component, indicating
the existence of a synergy between nZVI and Mg(OH)2.
Further mechanism analyses attested that Mg(OH)2 played a
crucial role by releasing OH− which can enhance the reduction
of Pb(II).
■ EXPERIMENTAL SECTION
Materials and Chemicals. All chemicals used in this study,
including magnesium sulfate (MgSO4·7H2O), sodium borohydride
(NaBH4), lead acetate (Pb[CH3COO]2·3H2O), ferrous sulfate
(FeSO4·7H2O), sodium hydroxide, acetic acid (CH3COOH), and
nitric acid (HNO3), were analytic grade purchased from Sinopharm
Chemical Reagent Shanghai Co. Ltd. and were used directly as
received without further purification. All solutions were prepared using
nanopure water (conductivity = 18 μΩ/m, Toc < 3 μg/L). A stock
solution of Pb(II) was prepared by dissolving 1.8306 g of lead acetate
(Pb[CH3COO]2·3H2O) into 1000 mL of nanopure water at a
volumetric flask, and a Pb(II) solution of different concentrations was
made by dilution of the stock solution.
Preparation of Mg(OH)2, nZVI and nZVI@Mg(OH)2 Compo-
site. Mg(OH)2 was prepared through facile precipitation method at
room temperature and atmospheric pressure. Briefly, NaOH (1 M)
solution was introduced into the same volume of MgSO4 (0.5M)
C3H8O3/H2O hybrid solution (15:85, v/v) dropwise, while stirring
vigorously through the titration, and it was continuously stirred for
another 6 h after the titration. After aging for 24 h, the precipitate was
collected by centrifugation and followed by washing with nanopure
water and absolute ethanol several times and then dried at 50 °C for
use.
A modified liquid phase sodium borohydride reduction method31
was employed to prepare Mg(OH)2 supported nZVI. In a typical
procedure, 0.416 g of Mg(OH)2 was dispersed in 75 mL of absolute
ethanol (ultrasonic dispersion for 5 min), 2.085 g of FeSO4·7H2O was
dissolved in 75 mL of nanopure water, and then the suspension and
Fe(II) solution were mixed in a 500 mL three-necked flask to make a
Fe(II) concentration of 0.05 M. Then the same volume of 0.25 M
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NaBH4 was added into the flask through titration with a rate of 3 mL/
min. Before and throughout the procedure, N2 was introduced to expel
the dissolved oxygen and keep an anaerobic environment. The flask
was stirred at 300 r/min using a mechanical stirrer, and the stirring was
continued for another 30 min after finishing the titration. The resulted
black paste was collected and washed with nanopure water and
absolute ethanol three times respectively, then dried in a vacuum oven
at 45 °C overnight, and stored for use. A composite with different Fe
content was synthesized through varying the ratio of Mg(OH)2 and
FeSO4·7H2O (the Fe mass fraction of composite used in following
experiments was 53.9% unless specially specified).
Unsupported nZVI was also prepared via the same procedure for
comparative study.
Characterizations and Measurements. X-ray diffraction
(XRD), scanning electron microscopy (SEM), transmission electron
microscopy (TEM), and BET N2 adsorption method were employed
to characterize the as-prepared Mg(OH)2, nZVI, and nZVI@
Mg(OH)2 composite.32 XRD analysis was conducted on a PANalytical
X’Pert PRO diffractometer with Cu KR radiation in the continuous
scanning mode at 40 kV, 40 mA from 2θ at 5 to 85° with a step size of
0.017°, and collection time of 20 s per step. SEM and TEM images
were obtained on a JSM-6700F scanning electron microscopy
equipped with an Oxford-INCA energy dispersive X-ray (EDS)
spectroscopy and a JEOL JEM2010 transmission electron microscopy
at 200 kV. BET surface area of the materials was measured with an
ASAP 2020 specific surface area and porosity analyzer (Micromeritics
Instrument Corp. U.S.).
Pb(II), Fe(II/III), and Mg(II) concentration in the liquid samples
collected from batch experiment was determined by atomic absorption
spectrometer (AAS, TAS-990FG, Purkinje General Analytical Instru-
ment corp. China), while Pb, Fe, and Mg element content of solid
samples as well as Fe mass fraction of raw composites was determined
by inductively coupled plasma-atomic emission spectrometry (ICP-
AES, Jobin Yvon Ulima2).
Pb(II) Removal: Batch Experiments. The optimal experimental
conditions were determined beforehand, details of the procedure were
described in the Supporting Information. Batch experiments for Pb(II)
removal, including performances of different materials and effects of
different initial Pb(II) concentration were conducted in a 250 mL
three-necked flask equipped with a mechanical stirrer at a speed of 300
r/min. The whole set of experiments were conducted at room
temperature and N2 environment (N2 was introduced 10 min before
the experiment started to expel the dissolved oxygen and throughout
the procedure to keep an anaerobic environment).
In order to compare the performance of Pb(II) removal by
Mg(OH)2, nZVI, and nZVI@Mg(OH)2, 50 mg of each was added into
100 mL of continuously stirred Pb(CH3COO)2 stock solution of 1000
mg/L. 3 mL of suspension was extracted at certain time intervals and
centrifuged to collect both liquid and solid samples. The liquid sample
was used for Pb(II), Fe(II/III), and Mg(II) concentration analysis
after being filtered by a syringe filter (0.22 μm) and acidized by HNO3
(0.01 M). The solid sample was dried for Pb, Fe, and Mg element
content analysis. The pH value of suspension was monitored and
recorded every 1 min during the experiments.
The effect of the initial Pb(II) concentration was tested by the same
procedure except the initial concentration was altered to 250, 500, 750,
and 1000 mg/L.
To investigate the feasibility toward actual industrial Pb(II)-bearing
wastewater, batch experiments were also conducted in acid Pb−Zn
mine tailing leachate which was analogous to industrial drainage in
terms of strong acidic and high multi-ion concentration solution
environment. The method was the same as the optimization
experiment.
■ RESULTS AND DISCUSSION
Characterization of the Materials. Figure 1 demonstrates
XRD patterns of nZVI, Mg(OH)2, and nZVI@Mg(OH)2. As
shown in Figure 1, the peaks of nZVI are well indexed as ferrite
(JCPDS: 00-006-0696), of which 2θ at 44.67, 65.02, and 82.33°
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Figure 1. XRD patterns of nZVI, nZVI@Mg(OH)2, and Mg(OH)2
(●, Fe; ■, Mg(OH)2) .
corresponds to [110], [200], and [211] directions of α-Fe,
respectively, indicating that unsupported nZVI has high purity
and good crystallographic degree.32,33 The mean grain size of
nZVI is calculated to be 22.6 ± 1.1 nm using the Scherrer
Figure 2. (a) SEM image of flower-like Mg(OH)2 spheres; (b) SEM image of nZVI@Mg(OH)2; (c) TEM image of nZVI@Mg(OH)2; (d) TEM
image of nZVI; (e) HAADF-STEM image of nZVI@Mg(OH)2; and corresponding EDS elemental mapping images.
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equation. The XRD pattern of as-prepared Mg(OH)2 is well
indexed as brucite (JCPDS: 00-007-0239), with a calculated
crystallite size of 21.6 ± 1.1, 31.1 ± 1.5, and 53.9 ± 2.7 nm in
the [001], [101], and [110] directions, respectively.29 However,
for nZVI@Mg(OH)2, only weak peaks at 18.53, 37.98, and
58.67° can be recognized, which are coincident with [001],
[101], and [110] diffraction peaks of Mg(OH)2. Besides, a peak
at 44.67° seems to be formed by broadening the [110] peak of
iron, probably due to the low crystallinity degree of iron, which
is similar to the previous literature.31 In addition, the specific
surface area is 11.6, 41.3, and 40.2 m2/g for nZVI, Mg(OH)2,
and nZVI@Mg(OH)2, respectively. The high specific surface
area is almost maintained after 53.9% Fe loading (determined
by ICP-AES), suggesting a well dispersion of nZVI particles.
Figure 2 shows the typical morphology of Mg(OH)2, nZVI,
and nZVI@Mg(OH)2. As shown in Figure 2a, as-prepared
Mg(OH)2 presents flower-like spheres with uniform size
around 10 μm. Enlarged micrograph (Figure S1) reveals that
the spheres are formed by interwoven Mg(OH)2 plates with a
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Figure 3. (a) Comparison of Pb(II) removal by nZVI@Mg(OH)2, nZVI, and Mg(OH)2 (dose: 500 mg/L, stirring speed: 300 r/min, initial
concentration: 1000 mg/L, initial pH: 6.86, temperature: 25 °C); (b) comparison of Pb(II) removal capacity and efficiency by nZVI@Mg(OH)2 and
weighted sum of the value by nZVI and Mg(OH)2 alone.

thickness of 10−20 nm. Morphology of nZVI@Mg(OH)2 in where QnZVI and QMg(OH)2 are the uptake amounts of Pb(II) by
Figure 2b,c reveals that nZVI particles are uniformly nZVI and Mg(OH)2 under the same experimental conditions.
immobilized on the surface of Mg(OH)2 plates, and nZVI wt %nZVI, wt % Mg(OH)2 are weight percentages of nZVI and
particles loaded on Mg(OH)2 have a diameter of 40−60 nm
Mg(OH)2 in the nZVI@Mg(OH)2 composite. As shown in
and a shell thickness of several nanometers.19,34 However,
Figure 3b, the values of capacity and efficiency are 1246 mg/g
similar to previous reports, we can see in Figure 2d that
and 62%, far less than that of nZVI@Mg(OH)2. Table 1 lists
unsupported nZVI particles tend to aggregate together, due to
van der Waals’ force and magnetic properties of the
Table 1. Comparison of Pb(II) Removal Performance of
particles.18,35 Enlarged TEM images (Figure S3) reveal that
nZVI@Mg(OH)2 with Other nZVI Based Materials
the nZVI particles have a diameter of approximately 25 nm,
Reported Previouslya
which is consistent with the calculated value through XRD
analysis. Moreover, a HAADF-STEM image of nZVI@Mg- specific surface area
(OH)2 and its corresponding EDS elemental mapping images (m2/g) capacity (mg/g)
are also presented in Figure 2e. Based on the O−K and Mg−K materials nZVI S.M. comp. nZVI S.M. comp.
signals and their distribution area, we find that the lamellar nZVI@Mg(OH)2 11.6 41.3 40.2 1718.4 775.4 1986.6
structure in designated area is Mg(OH)2 and Fe−K and Fe-L composite (this
study)
signal confirmed the particles belong to Fe (or its oxide), which
nZVI-Zeolite 12.3 1.0 83.4 806.0
certified the component of nZVI@Mg(OH)2 together with composite20
morphologic analysis.33 nZVI-Graphene 455.9 585.5
Pb(II) Removal from Water. The optimization experi- composite26
ments suggest that Pb(II) removal can be processed with a Sineguelas waste 3.9 35.6 63.5 225.0
supported nZVI36
neutral pH and 50% Fe content in composite (Figure S5).19
Kaolin supported 3.7 26.1 440.5
The study also shows that the initial Pb(II) concentration can nZVI17
barely influence the removal performance. Despite the fact that a
S.M. = support material, comp. = composite.
the initial concentration varies from 250 to 1000 mg/L, more
than 90% of Pb(II) is removed within 20 min for all samples.
Especially, when the initial concentration is lower than 750 mg/ the performance of some reported nZVI-based composite for
L, no Pb(II) is detected after 120 min (Figure S6). Pb(II) decontamination. Regardless of the varied experiment
Figure 3 presents the performance of Pb(II) removal by conditions in each study, to date, the nZVI@Mg(OH)2
Mg(OH)2, nZVI, and nZVI@Mg(OH)2 under the same composite in this work possesses the highest removal capacity.
optimal condition. As shown in Figure 3a, the Pb(II) In addition, we find that unsupported nZVI also exhibits a great
concentration decreases from the initial 1000 mg/L to 623.2, capacity (1718.4 mg/g) but still lower than that of nZVI@
141.8, and 6.8 mg/L after 120 min. The removal capacity of Mg(OH)2 composite. Therefore, we believe that the synergistic
Pb(II) for each material is calculated to be 775.4, 1718.4, and effect and good dispersion of nZVI particles on Mg(OH)2 can
1986.6 mg/g. The curves in Figure 3a show that the Pb(II) improve the removal performance effectively.18,20,26
Mechanisms of Pb(II) Removal by nZVI@Mg(OH)2. To
concentration decreases slowly for Mg(OH)2, while it occurs a
better understand the Pb(II) sequestration by the nZVI@
quick decline with fluctuant rate for unsupported nZVI. As for
Mg(OH)2 composite, the variations in phase, morphology,
nZVI@Mg(OH)2, the Pb(II) concentration drops more quickly
surface valence state of composite, and related metal ion
and ends with much lower residual concentration.16,18
concentrations were analyzed utilizing SEM/TEM, XRD, ICP-
Compared to Mg(OH)2 and nZVI, the removal performance AES, and high resolution X-ray photoelectron spectrometer
of the composite has obviously improved. To verify that the (HR-XPS).
improvement resulted from the synergistic effect of Mg(OH)2 Figure 4a illustrates the XRD pattern of the final solid sample
and nZVI, a weighted sum of capacity (as defined in formula 1) after treating 1000 mg/L Pb(II) solution. As shown in Figure
was calculated. 4a, the main phases are indexed as lead (Pb) and lead oxide
Q weightedsum = Q nZVI wt%nZVI + Q Mg(OH) wt%Mg(OH)2 (PbO), and there is no conspicuous peak attributed to nZVI
2 (1) and Mg(OH)2. Quantitative analyses by Rietveld spectrum
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Figure 4. (a) XRD pattern of collected solid material after contacting with Pb(II) solution (dose, 500 mg/L; stirring speed, 300 r/min; contact time,
120 min; initial concentration, 1000 mg/L; initial pH, 6.86; temperature, 25 °C; ■, Pb; ●, PbO); (b) trends of mass fractions (normalized) of
relative elements in solid phase; (c)trends of concentrations of relative metal ions in liquid phase during the experiment.
fitting reveal a hybrid phase of 47% Pb and 53% PbO,
suggesting that about half of Pb(II) is removed by reduction
under the given circumstance. To retell the details of the
sequestration process, variation of Pb, Fe, and Mg element
distribution in both solid phase and liquid phase are measured
during batch experiments. As shown in Figure 4b, Pb mass
fraction increases to over 90%, while Fe and Mg drop to 8.66%
and 1.2% for the final solid sample. Combined with XRD
analysis, the finally obtained solids are mainly comprised of
metallic lead and lead oxide. On the contrary, Figure 4c shows
that Pb(II) concentration in liquid samples decreases rapidly,
while Fe(II/III) and Mg(II) concentrations rise to a certain
level, due to the dissolution equilibrium of composite.
Figure 5 exhibits the morphology of nZVI@Mg(OH)2 before
and after reacting with Pb(II) solution. As shown in Figure
5c,d, the nZVI@Mg(OH)2 composite still presents a spherical
shape and intersection structure after reacting with low
concentration (250 mg/L) Pb(II) solution, and the lamellar
metallic lead or its compound is formed on the surface.
However, when the Pb(II) concentration is increased to 750
mg/L, the intersection structure is destroyed and replaced by
lead and its compound packing together closely, in spite of the
remaining spherical shape of nZVI@Mg(OH)2 composite. The
TEM micrograph (Figure 5b) also gives a clear version of the
status of nZVI particles after being treated with low
concentration (250 mg/L) Pb(II) solution, among which
some are intact and covered with thick-bedded target pollutant,
while others are corroded to be smaller-sized fragmentized
ones.
HR-XPS was employed to investigate the surface state of Fe,
O, and Pb. Figure 6 presents a detailed XPS survey of Fe 2p, O
1s, and Pb 4f regions. In Figure 6a, photoelectron peaks of the
Fe 2p region at 711 and 725 eV are attributed to the binding
energies of 2p3/2 and 2p1/2 of oxidized iron [Fe(III)], and the
weak peak at 706.7 eV suggests the existence of zerovalent iron
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(Fe 2p3/2), which would disappear after exposure to Pb(II)
solution due to extensive oxidization.34,37 As shown in Figure
6b, the photoelectron spectrum for the O 1s region can be
decomposed into three peaks at 529.9, 531.2, and 532.5 eV,
which represent the binding energies of different oxygen in O−,
OH−, and chemically or physically adsorbed water, respec-
tively.33,37 According to the fitting data recorded by XPS PEAK
software (Figure S8), the ratio of O−, OH−, and H2O varied
from 63.70%, 29.55%, and 6.75% to 49.54%, 42.68%, and
7.78%, respectively, after reaction. The decrease of the O− ratio
and the increase of the OH− ratio suggest that the hydroxide,
including lead hydroxide and ferric hydroxide, is generated. In
Figure 6c, photoelectron peaks at 136.7 and 138.2 eV
correspond to Pb0 and PbO.19,37 We can see from the figure
that the PbO phase is dominant in the final solid samples, while
Pb0 only accounts for 7.16%, which is different from that of the
XRD analyses. We believe that the limited penetration depth of
the XPS method and the susceptibility to oxidization of metallic
lead are responsible for those differences.16,18
As the pH value can be a reliable tracer of the reactions
during Pb(II) removal, the variation of the pH value was
recorded throughout the experiment. As shown in Figure 7a
(and Figure S7), without exception, a decline of pH emerges in
all nZVI involved processes but is absent when dosed with
Mg(OH)2 alone. This phenomenon can be explained by the
hydroxylation of Fe(II/III), which can be derived from the
following paths: (a) dissolution of iron oxides/hydroxides on
the nZVI shell, (b) reaction between zerovalent iron and
water,38 and (c) reduction of Pb(II) by zerovalent iron.16,33
Since the experiments were conducted under N2 environment,
we presume that the anaerobic environment was well
controlled, and the major reactions are listed as eqs 2−6.
Mg(OH)2 (s) → Mg 2 + + 2OH− (2)
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Figure 5. (a) SEM image of nZVI@Mg(OH)2; (b) TEM image; (c and d) SEM images of collected solid material after contacting with low
concentration of Pb(II) solution (250 mg/L); (e and f) SEM images of collected solid material after contacting with high concentration of Pb(II)
solution (750 mg/L).
Pb2 + + 2OH− → Pb(OH)2 (s) (3)
Pb2 + + Fe 0(s) → Fe 2 + + Pb0 (s) (4)
Fe2 + + 2H 2O → Fe(OH)2 (s) + 2H+ (5)
Fe0(s) + 2H 2O → Fe 2 + + H 2(g) + 2OH− (6)
Based on the analysis above, a mechanism of Pb(II) removal
by nZVI@Mg(OH)2 was proposed. In general, Pb(II) was
sequestrated through a synergistic process, including adsorp-
tion, reduction, ion exchange reaction, and subsequent
precipitation.16,18,19,33,37 According to the variation of the
solution pH value, the removal of Pb(II) experienced three
stages as shown in Figure 7b.
First, Pb(II) was attracted to the surface of nZVI particles
and Mg(OH)2, and then ion exchange reaction was initiated
due to the dissolution of Mg(OH)2 (eq 2). At the same time,
Pb(II) was partly reduced to Pb0 by nZVI particles (eq 4), and
the hydroxylation of Fe(II) (eq 5) would be triggered when it
was accumulated to a certain concentration. The competition of
above reactions resulted a slight ascendant of pH value.
Second, the reduction of Pb(II) became dominant, and thus
the pH saw a rapid decline caused by the hydroxylation of
Fe(II). pH changes of different initial Pb(II) concentrations
reveal that a higher initial Pb(II) concentration led to an earlier,
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larger extent of pH drop (Figure S7), indicating that the pH
decline is indeed a consequence of Pb(II) reduction.
Third, The dissolution of Mg(OH)2 continued (eq 2), and
the reaction between iron and water (eq 6) proceeded slowly
and induced a jump of pH value. Therefore, Pb(II) could be
precipitated during this stage (eq 3).
The mechanism analyses suggest that Mg(OH)2 plays an
essential role in Pb(II) immobilization for its dispersive,
supportive, and nZVI particle aggregate-preventive function as
well as its intense inherent affinity to Pb(II). More significantly,
a mutual stimulation between reactions 2 and 4 can occur; thus,
the hydroxies provided by Mg(OH)2 can dramatically promote
the role of nZVI as a reducer. In return, nZVI accelerates the
dissolution of Mg(OH)2. The multifunction of Mg(OH)2
makes it a good assistant for nZVI.
Remove Pb(II) from Acid Pb−Zn Mine Tailing
Leachate. The results of Pb(II) removal from acid Pb−Zn
mine tailing leachate by the nZVI@Mg(OH)2 composite are
listed in Table 2. To meet the discharge standard (1.0 mg/L),
we varied the dosage from 1000 to 10 000 mg/L and found that
the residual concentration of Pb(II) and Zn(II) dropped to
0.22 and 14.2 mg/L, respectively. When the dosage was 7000
mg/L, it corresponded to a removal efficiency of 99.9% and
90.0%. The results certified that Pb(II) could be sequestrated
effectively by this composite even under complicated solution
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Figure 6. XPS survey of (a) the Fe 2p region, (b) the O 1s region of solid samples before and after treating Pb(II) solution (1000 mg/L), and (c)
XPS survey of the Pb 4f region of the final solid sample.

Figure 7. (a) Changes of solution pH during Pb(II) removal by different materials (initial Pb(II) concentration, 1000 mg/L); (b) stages of pH
variation during Pb(II) removal by nZVI@Mg(OH)2 (initial Pb(II) concentration, 1000 mg/L).

Table 2. Removal Performance Towards Acid Pb−Zn Mine

Tailing Leachate
■ CONCLUSIONS
In summary, a new Fe0 containing composite (nZVI@
Pb(II) Zn(II) pH Mg(OH)2) was prepared, characterized, and applied to remove
initial concentration (mg/L) 698.1 201.5 4.8
Pb(II). The morphology and phase analyses demonstrated that
after neutralized (mg/L) 412.0 142.8 7.0
nZVI particles were successfully loaded on the surface of the
ultimate concentration (mg/L) 0.22 14.2 7.2
self-supported flower-like Mg(OH)2. The results of Pb(II)
uptake amount (mg/g) 58.4 18.2 -
removal present a superb capacity (1986 mg/g) and large
removal efficiency (%) 99.9 90.0 -
kinetic removal rate (94% uptake within 15 min). We also
explored the mechanisms of Pb(II) deprivation, which revealed
that Mg(OH)2 can facilitate the sequestration by alleviating
aggregation of nZVI particles, enhancing Pb(II) reduction and
environment. Besides, the outlet pH value was relatively acting as an absorbent itself. The authors of this article believe
that it is the multirole of Mg(OH)2 and the synergistic effect
moderate compared to that made by the traditional alkali between nZVI and Mg(OH)2 that lead to the exceptional
precipitation method (as high as pH 10). performance of the composite. We think the results of this
7967 DOI: 10.1021/am509184e
ACS Appl. Mater. Interfaces 2015, 7, 7961−7969
ACS Applied Materials & Interfaces
work could provide an alternative technique for treating Pb(II)-
bearing wastewater.
■
ASSOCIATED CONTENT
*
S Supporting Information
Optimization of operation conditions, Pb(II) removal test in
acid Pb−Zn mine tailing leachate, effect of initial concentration,
extra SEM and TEM images, and XPS fitting photoelectron
spectra. This material is available free of charge via the Internet
at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +86 591 83792630. Fax: +86 591 83705474. E-mail:
zlin@fjirsm.ac.cn; zlin@scut.edu.cn.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Financial support was provided by the National Basic Research
Program of China (2013CB934302 and 2014CB932101), the
Outstanding Youth Fund (21125730), the “Strategic Priority
Research Program” of the Chinese Academy of Sciences
(XDA09030203), the National Science Foundation Grant
(21477128), and the Technology Key Project of Fujian
Province (2013H0058).
■
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7969 DOI: 10.1021/am509184e

ACS Appl. Mater. Interfaces 2015, 7, 7961−7969